Propyne → 4-(Tert-butyl-diphenyl-silanyloxymethyl)-2-prop-1-ynyl-pyridine

HRID 402876

反応式

HRID 402876 の反応式
[C:1]([SiH2:5][O:6][C:7]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:8]1[CH:13]=[CH:12][N:11]=[C:10](Cl)[CH:9]=1)([CH3:4])([CH3:3])[CH3:2].[C:27]1(P(C2C=CC=CC=2)C2C=CC=CC=2)[CH:32]=CC=C[CH:28]=1.C(NCC)C.C#CC.C([O-])(O)=O.[Na+]>[Cl-].[Cl-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd+2].[Cu]I.CN(C)C=O>[C:1]([SiH2:5][O:6][C:7]([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:8]1[CH:13]=[CH:12][N:11]=[C:10]([C:28]#[C:27][CH3:32])[CH:9]=1)([CH3:4])([CH3:3])[CH3:2]

参加物

9

反応物 5

HCID 6335PropyneHCID 8021DiethylamineHCID 11776TriphenylphosphineHCID 516892Sodium BicarbonateHCID 1317297514-(Tert-butyl-diphenyl-silanyloxymethyl)-2-chloro-pyridine

生成物 1

HCID 1317297504-(Tert-butyl-diphenyl-silanyloxymethyl)-2-prop-1-ynyl-pyridine収率 104.4%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 84124Bis(triphenylphosphine)palladium chloride触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
120 °C

実験手順

A reaction tube is charged under an atmosphere of argon with 4-(tert-butyl-diphenyl-silanyloxymethyl)-2-chloro-pyridine (9.47 g, 24.79 mmol), palladium(II)-bis(triphenylphosphine)-dichloride (1.78 g, 2.49 mmol, 0.1 equiv), copper(I) iodide (477 mg, 2.49 mmol, 0.1 equiv), and triphenylphosphine (3.94 g, 14.9 mmol, 0.6 equiv). The tube is degassed by alternating three times between vacuum and argon. Diethylamine (39 ml) and N,N-dimethylformamide (2.0 ml), and propyne (50% in THF, 10.1 g, 247 mmol, 10 equiv) are added under an argon atmosphere. The tube is sealed, and the reaction mixture is heated under microwave irradiation for 20 minutes at 120° C. After cooling, the reaction mixture is poured into a semi-concentrated aqueous solution of NaHCO3. After three extractions with EtOAc, the combined organic layers are washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. Purification via flash chromatography (gradient from hexane/EtOAc 100:0 to 50:50) affords the title compound (6.0 g, 63%). 1H NMR (400 MHz, d6-DMSO): δ=8.41 (d, J=5.0 Hz, 1H), 7.57-7.55 (m, 4H), 7.43-7.32 (m, 11H), 7.27 (d, J=5.0 Hz, 1H), 4.72 (s, 2H), 1.99 (s, 3H), 0.98 (s, 9H). MS (ES+): 386 (M+H)30.

後処理

  1. customThe tube is degassed
  2. customThe tube is sealed
  3. temperatureAfter cooling
  4. extractionAfter three extractions with EtOAc
  5. washthe combined organic layers are washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customPurification via flash chromatography (gradient from hexane/EtOAc 100:0 to 50:50)

出典と根拠

ORDレコード
ord-4875cbdd8d4242629271ee9ba61856ef
出典データセット
uspto-grants-2014_06
特許番号
US08742132B2

関連ノート

読み込み中…